Silicon-containing organic fluoropolymers and use of the same

ABSTRACT

Novel silicon-containing organic fluoropolymers which are appliable to materials over a wide range and which have excellent antifouling property. The silicon-containing organic fluoropolymer of the invention is represented by the general formula and has a number average molecular weight of from 5×10 2  to 1×10 5 :                    
     wherein Rf represents perfluoroalkyl; Z represents fluoro or trifluoromethyl; a, b, c, d and e each independently represent 0 or an integer of 1 or above, provided that a+b+c+d+e is not less than 1 and the order of the repeating units parenthesized by subscripts a, b, c, d and e occurring in the formula is not limited to that shown; Y represents hydrogen or alkyl containing 1 to 4 carbon atoms; X represents hydrogen, bromo or iodo; R 1  represents hydroxy or a hydrolyzable substituent group; R 2  represents hydrogen or a monovalent hydrocarbon group; 1 represents 0, 1 or 2; m represents 1, 2 or 3; and n represents an integer of 2 or above.

TECHNICAL FIELD

The present invention relates to a novel silicon-containing organicfluoropolymer never heretofore described in the literatures, and to usethereof. More particularly, the present invention relates to asilicon-containing organic fluoropolymer that has excellent solventresistance and chemical resistance and is very effective in preventingfouling of the surfaces of various substrates, and to use thereof.

BACKGROUND ART

A variety of organic fluoropolymers comprising a perfluoropolyetherchain have unique functional characteristics such as water and oilrepellency and low refractive index as well as excellent heat resistanceand chemical resistance. They are thus known as polymers of great valueadded and finding applications in a broad range.

Meanwhile, silane compounds represented by the general formula;BSi(R)_(3−r)D_(r) [wherein B represents an organic residue reactive toorganic compounds including polymers; D represents halogen or alkoxy; Rrepresents alkyl; r represents 1, 2 or 3] are generally known as silanecoupling agents and have been used as surface-treating agents forvarious materials. In addition, the above moiety-terminated polymers areknown to undergo hydrolysis by water at room temperature, therebyprogressing condensation polymerization or crosslinking for curing[Encyclopedia of Chemical and Technology, Vol. 12, pp. 464 to 569,1970].

Also known are attempts to modify organic fluoropolymers with suchsilane compounds. For example, fluorosilicone, fluoroolefin-vinylsilanecopolymers, α, ω-bis(dialkyl-chlorosilyl)polyfluoroalkanes, etc. can bementioned as examples [Journal of Polymer Science, Part-A, Vol. 10, No.3, pp. 947 to 953].

Japanese Kokai Publication Hei-1-294709 discloses an organicfluoropolymer containing such a vinylsilane unit. This polymer, whichhas both water repellency and antifouling property, is claimed to beused effectively, for example, in an automotive outside plate coating:

Japanese Kokai Publication Hei-5-339007 discloses a fluorine-containingorganosilicon compound as an example of application of said silanecompound to an organic fluoropolymer. This compound is characterized inthat said silane compound is linked to a perfluoropolyether chain of anorganic fluoropolymer and that the carbon atom to which said silanecompound is bound is iodinated. This compound, which has low surfaceenergy, is said to be of value as a material for the production oftextile finishing agents, mold releasing agents, release agents orantifouling paints.

However, the silane compound-containing organic fluoropolymers so farknown are not sufficiently antifouling because only one reactive siliconatom is available at the terminus of the perfluoropolyether chain. Theterm “antifouling” is used herein to mean both property to rejectdeposition of fouling matter and property to readily release a depositedfouling matter on washing.

Meanwhile, metal, glass and plastic materials are in broad use as asubstrate of automotive parts, OA equipments, household electricalappliances, and among other applications. The exposed surface of thosesubstrates tend to be contaminated by deposits of the airborne dustparticles in the car interior or the office or other room, by oilysubstances originating from food or machine oil, or by fingerprints onhandling. Therefore, those substrates must be somehow protected againstsuch fouling and, in addition, rendered ready to wipe off fouling andother deposits.

As an antifouling technology for a glass surface, Japanese KokaiPublication Hei-1-126244 and other literatures disclose a method whichcomprises coating a glass surface directly with a polymer material suchas polydimethylsiloxane or dipping the substrate in such a treatingagent for forming a film. Another technology is also known for forming afluorine-containing unimolecular film on a glass surface bychemisorption.

As an antifouling technology for a metal surface, Japanese KokokuPublication Hei-7-53913 discloses a method which comprises forming achromate layer containing a silica sol type silane coupling agent on topof a usual galvanized steel surface and then forming a thin top filmusing an isocyanate coating composition thereon to provide an organiccomposite-plated steel sheet.

However, those conventional treatments are not sufficiently effective inprotecting substrates against attachment of oily contaminants. Moreover,the substrate surface, which are directly touched by hand, are liable tobe contaminated by fingerprints, which cannot be easily wiped off.

Furthermore, those antifouling properties is drastically handicappedunder severe conditions such as outdoor exposure so that thosetechnologies are not fully satisfactory in terms of weatherability. Inaddition, the inevitable use of an expensive fluorine-containing organicsolvent in a large amount is a drawback from the standpoint ofproduction cost.

Meanwhile, the surface of substrates used in mobile equipment such asmotor vehicles, rolling stock, aircraft, ships, etc., and home and otherbuildings are exposed to wind and rain during their use. Moreover, indistricts frequented by heavy snowfalls or extremely cold climates,particularly in winter months, this surface remain directly exposed tosnow and ice for a long time. Furthermore, in special establishmentssuch as cold experiment facilities and certain household electricalappliances such as refrigerators, too, their members are partly exposedto very low temperatures so that waterdrops and moisture in the air aredeposited as ice.

When ice is deposited on the surface of car substrate, its functions areadversely affected. Taking a windshield glass as an example, icinginterferes with the driver's sight and may cause an accident. When iceis deposited on certain members of the refrigerator and so on, itscooling efficiency is sacrificed to increase a waste of electric energy.

Japanese Kokai Publication Hei-3-158794 discloses a technology forperforming an antifogging treatment, which comprises forming ahydrophilic film.

Japanese Kokai Publication Hei-1-126244 discloses a technology forimparting water repellency to a glass surface, which comprises coatingthe surface directly with an organosilicone compound such aspolydimethylsiloxane or dipping it in such a treating agent for forminga film.

Japanese Kokai Publication Hei-4-338147 and Japanese Kokoku PublicationSho-63-24554 disclose a technology for imparting water repellency to aglass surface, which comprises forming a fluoroalkyl-containing siliconoxide film on the surface by chemisorption or in a sol-gel process usinga fluoroalkylsilane compound.

However, said antifogging treatment comprising formation of ahydrophilic film is not effective in preventing deposition of ice. Insaid technology which comprises forming an organosilicone compound filmon a glass surface, there is much possibility that this film will beexfoliated in its use because this film is not chemically bound toglass. It is thus poor in durability. Said technology which comprisesforming a fluoroalkyl-containing silicon oxide film on a glass surfaceinsures sufficient durability but fails to provide necessary lubricity.Moreover, those technologies as used independently or in combination arenot effective in preventing icing even if water repellency is secured.

For preventing icing, it is necessary in the first place to insure thaticing will not occur or be hard to occur on a substrate surface inquestion. However, it is also important to make it easy to removedeposits of ice once formed, in view of the fact that considerabledifficulties are involved in removing deposits of ice once formed.Therefore, an anti-icing agent is in demand, which is not only capableof preventing icing itself but allows deposits of ice to be removed withease.

On the other hand, glass, which possess high optical transmission,insulation property and ornamental characteristic, have been used in avariety of applications such as residential window panes and otherarchitectural members, vehicle members such as car and rolling stock,windshield members for ships and airplanes, among others. In thoseapplications, glass is used in places exposed to the outdoor environmentand is often exposed to rain or come in contact with seawater orcontaminated water. Moreover, windshield glasses of cars and so onnecessitate an important function to secure clear sight. For maintainingsufficient optical transmission, the glass itself has been required tohave the property to repel rainwater or the like (this property isreferred to as water repellency in this specification).

However, in said technology which comprises forming an organosiliconecompound film on a glass surface, there is much possibility that thisfilm will be exfoliated in its use because this film is not chemicallybound to glass. It is thus poor in durability. Said technology whichcomprises forming a fluoroalkyl-containing silicon oxide film on a glasssurface insures sufficient durability but fails to provide necessarylubricity and antitackiness. For instance, when the treated glass isused as the windshield of a car, the wipers will emit a beeping noise.

SUMMARY OF THE INVENTION

The first aspect of the present invention, in view of theabove-described state of the art, has for its object to provide a novelsilicon-containing organic fluoropolymer which is appliable to materialsover a wide range and which has excellent antifouling property.

Thus, the first aspect of the present invention is directed to asilicon-containing organic fluoropolymer represented by the generalformula (I), which comprises having a number average molecular weight offrom 5×10² to 1×10⁵:

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R² represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; m represents 1, 2 or 3; and nrepresents an integer of 2 or above.

The second aspect of the present invention, in view of theabove-described state of the art, has for its object to provide anantifouling substrate which is highly resistant to oily fouling matter,particularly fingerprint.

Thus, the second aspect of the present invention is directed to anantifouling substrate which comprises a substrate and, as formed on thesurface thereof, a layer of a silicon-containing organic fluoropolymerrepresented by the general formula (Ix) and having a number averagemolecular weight of from 5×10² to 1×10⁵:

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R² represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; m represents 1, 2 or 3; andn_(x) represents an integer of 1 or above.

The third aspect of the present invention, in view of theabove-described state of the art, has for its object to provide asurface-treating method for imparting sufficient and long-lastingantifouling property and sufficient weatherability to a substrate.

Thus, the third aspect of the present invention is directed to asurface-treating method for a substrate, which comprises coating thesubstrate surface with a treating solution comprising (1) asilicon-containing organic fluoropolymer represented by the abovegeneral formula (Ix), (2) a fluorine-containing organic solvent and (3)a silane compound [excepting said silicon-containing organicfluoropolymer (1)].

The fourth aspect of the present invention, in view of theabove-described state of the art, has for its object to provide asurface-treating composition for imparting sufficient and long-lastingantifouling property and sufficient weatherability to a substrate, whichhas an economic advantage.

Thus, the fourth aspect of the present invention is directed to asurface-treating composition which comprises (1) a silicon-containingorganic fluoropolymer of the above general formula (Ix), (2) afluorine-containing organic solvent and (4) an organic solvent[excepting said fluorine-containing organic solvent (2)].

The fifth aspect of the present invention, in view of theabove-described state of the art, has for its object to provide ananti-icing agent which is effective in preventing deposition of ice.

Thus, the fifth aspect of the present invention is directed to ananti-icing agent which comprises a silicon-containing organicfluoropolymer represented by the above general formula (Ix).

The sixth aspect of the present invention, in view of theabove-described state of the art, has for its object to provide a glassmember having not only sufficient durability, surface lubricity andsurface antitackiness but also excellent water repellency.

Thus, the sixth aspect of the present invention is directed to awater-repellent glass member which comprises a glass substrate and, asformed on the glass surface, a layer of a silicon-containing organicfluoropolymer represented by the above general formula (Ix).

DETAILED DESCRIPTION THE INVENTION

The first aspect of the present invention is now described in detail.

The Rf in the above general formula (I) representing saidsilicon-containing organic fluoropolymer according to the first aspectof the invention is virtually any perfluoroalkyl group capable of beinga constituent of an organic fluoropolymer. It includes but is notlimited to straight-chain or branched perfluoroalkyl groups containing 1to 16 carbon atoms. Preferred are CF₃—, C₂F₅—, and C₃F₇—.

The Z in the above general formula (I) may be whichever of fluoro andtrifluoromethyl.

The a, b, c, d and e in the above general formula (I) respectivelyrepresent the numbers of repetitions of the perfluoropolyether unitsconstituting the main chain of the silicon-containing organicfluoropolymer according to the first aspect of the present invention.They are not limited provided that they each independently represent 0or an integer of 1 or above and that a+b+c+d+e is not less than 1. Eachof them is preferably 0 to 200. Each of them is more preferably 0 to 50,taking into consideration the number average molecular weight of thesilicon-containing organic fluoropolymer according to the first aspectof the invention, which is to be described hereinafter. The a+b+c+d+e ispreferably 1 to 100.

The order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the above general formula (I) is only presented forconvenience's sake; however, in view of the conventional arrangement ofperfluoropolyether chains, the order of combination of those repeatingunits is not limited to the above order.

The Y in the above general formula (I) represents hydrogen or alkylcontaining 1 to 4 carbon atoms. There is no particular limitation onsaid alkyl containing 1 to 4 carbon atoms but it can include methyl,ethyl, propyl, butyl and the like, regardless of whether straight-chainor branched. The X in the above general formula (I) represents hydrogen,bromo or iodo. When the X is bromo or iodo, the silicon-containingorganic fluoropolymer shows enhanced radical reactivity; therefore, thisis advantageous in causing it to be linked to other compounds bychemical bonding.

The 1 in the above general formula (I) represents the number of carbonatoms of the alkylene group interposed between the terminal carbon atomof the perfluoropolyether chain and the silicon atom. It represents 0, 1or 2, preferably 0.

The m in the above general formula (I) represents the number of thesubstituent R¹ bound to silicon in the silicon-containing organicfluoropolymer according to the first aspect of the invention. Itrepresents 1, 2 or 3. The substituent R² is bound to said silicon in itsvalence position or positions in which the R¹ is not present.

The R¹ represents hydroxy or a hydrolyzable substituent. There is noparticular limitation on species of said hydrolyzable substituent.Preferred, however, are halogen, —OR³, —OCOR³, —OC(R³)═C(R⁴)₂,—ON═C(R³)₂ and —ON═CR⁵ (wherein R³ represents an aliphatic hydrocarbongroup or an aromatic hydrocarbon group; R⁴ represents hydrogen or analiphatic hydrocarbon group containing 1 to 4 carbon atoms; and R⁵represents a bivalent aliphatic hydrocarbon group containing 3 to 6carbon atoms), among others. More preferred are chloro, —OCH₃ and—OC₂H₅.

The R² represents hydrogen or a monovalent hydrocarbon group. There isno particular limitation on species of said monovalent hydrocarbongroup. It preferably includes but is not limited to monovalent aliphaticsaturated hydrocarbon groups such as methyl, ethyl, propyl and butyl,inclusive of both straight-chain and branched groups.

The number average molecular weight of the silicon-containing organicfluoropolymer according to the first aspect of the present invention is5×10² to 1×10⁵. If it is less than 5×10², the polymer will be lacking incharacteristics of a polymer and of no practical use. On the other hand,if it exceeds 1×10⁵, the polymer will be of poor processability.Therefore, the above range should be adhered to. The preferred numberaverage molecular weight is 1×10³ to 1×10⁴ .

The essential feature of the first aspect of the present inventionresides in the number of the n in the above general formula (I). The nin the general formula (I) represents the number of reactive siliconatoms contained in the silicon-containing organic fluoropolymeraccording to the first aspect of the invention. In the first aspect ofthe invention, the n represents an integer of 2 or above. If it is notgreater than 1, antifouling property as the unique effect of the firstaspect of the invention will not be sufficiently expressed. Therefore,the n should be limited to 2 or above. There is no particular upperlimit to the number of the n only if it is 2 or above but the preferrednumber is 2 to 10.

The silicon-containing organic fluoropolymer according to the firstaspect of the present invention is available as a mixture when aconventional production technology is used for its production. Theparameter g in the following general formula (Ia) represents the numberof reactive silicon atoms contained in a mixture of thesilicon-containing organic fluoropolymers according to the first aspectof the invention. In the mixture of the silicon-containing organicfluoropolymer according to the first aspect of the invention, the grepresents 0 or an integer of 1 or above and the mean value of the g insaid mixture is greater than 1. If the mean value of the g is notgreater than 1, the antifouling property of the polymer will be poor inuse as an antifoulant. Therefore, it should be in excess of 1. Thepreferred mean value of the g is 1.3 to 3 and the particularly preferredone is 1.5 to 2.5.

The preferred silicon-containing organic fluoropolymer for use in thefirst aspect of the present invention includes, for example, a polymerrepresented by the following general formula (II):

wherein p represents an integer of 1 or above; Y, X, R¹, R², 1, m and nare the same as defined above.

The preferred mixture of the silicon-containing organic fluoropolymersin the first aspect of the present invention includes, for example, amixture of polymers represented by the following general formula (IIa):

wherein p represents an integer of 1 or above; Y, X, R¹, R², 1, m and gare the same as defined above.

The p in the above general formula (II) and (IIa) is not particularlylimited only if it is an integer of 1 or above. It is preferably 1 to200. It is more preferably 1 to 50, taking into consideration the numberaverage molecular weight of the silicon-containing organic fluoropolymeraccording to the first aspect of the invention.

The silicon-containing organic fluoropolymer according to the firstaspect of the invention can be typically obtained from an ordinarilycommercial perfluoropolyether by, for example, iodinating its terminusand then, for example, reacting it with a vinylsilane compoundrepresented by the following general formula, wherein Y, R¹, R², 1 and mare as the same defined above.

The silicon-containing organic fluoropolymer according to the firstaspect of the invention can be used as a universal sealant, coatingagent, coupling agent or the like in the fields of housing members andautomotive parts. Furthermore, for surface-antifouling purposes, it canbe applied advantageously to various substrates such as optical lenses,spectacle lenses, glass products, metallic parts, ceramic products andorganic products.

To the silicon-containing organic fluoropolymer according to the firstaspect of the invention can be added in use finely divided powders offillers such as silica, alumina, titanium dioxide, carbon, cement, etc.;alkoxides of titanium, aluminum, silicon, etc.; or fluororesins such aslow-molecular-weight polytetrafluoroethylene,tetrafluoroethylene-hexafluoropropylene copolymer, etc. as a hardnessregulator or extender. In addition, a conventional crosslinking agentmay be added for regulating hardness.

The substrate surface can be coated with the silicon-containing organicfluoropolymer for forming a layer from said silicon-containing organicfluoropolymer. The coating technology used includes but is not limitedto spray coating, spin coating, dip coating, roll coating, gravurecoating, and curtain flow coating, among other coating techniques.

Dilution of the polymer with a solvent beforehand makes coating easier.There is no particular limitation on species of said solvent used forthis purpose. For example, perfluorohexane, perfluoromethylcyclohexane,perfluoro-1,3-dimethylcyclohexane, dichloropentafluoropropane (HCFC225),etc. can be mentioned.

The second aspect of the present invention is now described in detail.

The substrate to which the antifouling substrate of the second aspect ofthe invention can be applied includes but is not limited to glass,resin, metal, ceramics, wood, porcelain, stone and leather.

Said glass substrate includes virtually all kinds of glass for use asshow windows, mirrors, water tanks, window glass panes, cupboardshelves, glass cases, etc.

There is no particular limitation on said resin substrate. Thus, notonly natural resins but also synthetic resins are included. Said naturalresin includes but is not limited to cellulose and Japanese lacquer.Said synthetic resin includes but is not limited to polyamide resin,polyacrylate resin, poly(amide imide) resin, poly(vinyl acetate) resin,poly(vinyl chloride) resin, phenolic resin, urea resin, melamine resin,epoxy resin, and polyester resin.

There is no particular limitation on species of said metal. For example,iron, zinc, lead, copper and aluminum can be mentioned.

In accordance with the second aspect of the invention, a layer of thesilicon-containing organic fluoropolymer, which is represented by saidgeneral formula (Ix) and has a number average molecular weight of from5×10² to 1×10⁵, is formed on the surface of said substrate.

The Rf in the above general formula (Ix) may be substantially anyperfluoroalkyl group ordinarily constituting an organic fluoropolymer.It can include but is not limited to straight-chain or branched groupscontaining 1 to 16 carbon atoms. Preferred are CF₃—, C₂F₅—, and C₃F₇—.

The Z in the above general formula (Ix) may be whichever of fluoro andtrifluoromethyl.

The a, b, c, d and e in the above general formula (Ix) respectivelyrepresent the numbers of repetitions of the perfluoro(poly)ether unitsconstituting the main chain of the silicon-containing organicfluoropolymer according to the second aspect of the present invention.They are not limited provided that they each independently represent 0or an integer of 1 or above and that a+b+c+d+e is not less than 1. Eachof them is preferably 0 to 200. Each of them is more preferably 0 to 50,taking into consideration the number average molecular weight of thesilicon-containing organic fluoropolymer according to the second aspectof the invention, which is to be described hereinafter. The a+b+c+d+e ispreferably 1 to 100.

The order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the above general formula (Ix) is only presented forconvenience's sake; however, in view of the conventional arrangement ofperfluoropolyether chains, the order of combination of those repeatingunits is not limited to the above order.

The Y in the above general formula (Ix) represents hydrogen or alkylcontaining 1 to 4 carbon atoms. There is no particular limitation onsaid alkyl containing 1 to 4 carbon atoms but it can include methyl,ethyl, propyl, butyl and the like, regardless of whether straight-chainor branched. The X in the above general formula (Ix) representshydrogen, bromo or iodo. When the X is bromo or iodo, thesilicon-containing organic fluoropolymer shows enhanced radicalreactivity; therefore, this is advantageous in causing it to be linkedto other compounds by chemical bonding.

The 1 in the above general formula (Ix) represents the number of carbonatoms of the alkylene group interposed between the terminal carbon atomof the perfluoropolyether chain and the silicon atom. It represents 0, 1or 2, preferably 0.

The m in the above general formula (Ix) represents the number of thesubstituent R¹ bound to silicon in the silicon-containing organicfluoropolymer according to the second aspect of the present invention.It represents 1, 2 or 3. The substituent R² is bound to said silicon inits valence position or positions in which the R¹ is not present.

The R¹ represents hydroxy or a hydrolyzable substituent. There is noparticular limitation on species of said hydrolyzable substituent.Preferred, however, are halogen, —OR³, —OCOR³, —OC(R³)═C(R⁴)₂,—ON═C(R³)₂ and —ON═CR⁵ (wherein R³ represents an aliphatic hydrocarbongroup or an aromatic hydrocarbon group; R⁴ represents hydrogen or analiphatic hydrocarbon group containing 1 to 4 carbon atoms; and R⁵represents a bivalent aliphatic hydrocarbon group containing 3 to 6carbon atoms), among others. More preferred are chloro, —OCH₃ and—OC₂H₅.

The R² represents hydrogen or a monovalent hydrocarbon group. There isno particular limitation on species of said monovalent hydrocarbongroup. It preferably includes but is not limited to monovalent aliphaticsaturated hydrocarbon groups such as methyl, ethyl, propyl and butyl,inclusive of both straight-chain and branched groups.

The n_(x) in the above general formula (Ix) represents an integer of 1or above. There is particularly no upper limit on the value of the n_(x)but it is preferably an integer between 1 and 10 in order that theobject of the second aspect of the invention may be accomplished.

The n_(x) represents an integer in the above general formula (Ix);however, the silicon-containing organic fluoropolymer for use in thesecond aspect of the invention may be a mixture of the polymers of thegeneral formula (Ix) wherein n_(x)s represent a plurality of differentintegers. When the silicon-containing organic fluoropolymer (Ix) is sucha mixture, the n_(x) can be expressed in mean. The mean value of then_(x) is preferably 1.3 to 3 and more preferably 1.5 to 2.5 inconsideration of the object of the second aspect of the invention.

The number average molecular weight of the silicon-containing organicfluoropolymer is from 5×10² to 1×10⁵. If it is less than 5×10², thepolymer will be lacking in characteristics of a polymer and of nopractical use. On the other hand, if it exceeds 1×10⁵, the polymer willbe poor in processability. Therefore, the above range should be adheredto. It preferably is from 1×10³ to 1×10⁴.

The preferred silicon-containing organic fluoropolymer includes but isnot limited to a polymer represented by the following general formula(IIx):

wherein p represents an integer of 1 or above; Y, X, R¹, R², 1, m andn_(x) are the same as defined above.

Referring to the above general formula (IIx), there is no particularlimitation on the value of the p only if it is 1 or above. The p ispreferably between 1 and 200. It is more preferably between 1 and 50 inconsideration of the number average molecular weight of thesilicon-containing organic fluoropolymer according to the second aspectof the invention.

The above silicon-containing organic fluoropolymer can be obtained, forexample, by iodinating the terminus of an ordinarily commercialperfluoropolyether and then reacting it with, for example, a vinylsilanecompound represented by the following general formula, wherein Y, R¹,R², 1 and m are the same as defined above.

To said silicon-containing organic fluoropolymer can be added in usefinely divided powders of fillers such as silica, alumina, titaniumdioxide, carbon, cement, etc.; alkoxides of titanium, aluminum, silicon,etc.; or fluororesins such as low-molecular-weightpolytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylenecopolymer, etc. as a hardness regulator or extender. In addition, aconventional crosslinking agent may be added for regulating hardness.

The substrate surface can be coated with the silicon-containing organicfluoropolymer for forming a layer from said silicon-containing organicfluoropolymer. The coating technology used includes but is not limitedto the various coating techniques mentioned for the first aspect of thepresent invention.

Dilution of the polymer with a solvent facilitates coating. There is noparticular limitation on species of said solvent used for this purpose.For example, the solvents mentioned in connection with the correspondingprocedure in the first aspect of the invention can be employed.

The thickness of a layer of the silicon-containing organic fluoropolymerin the antifouling substrate according to the second aspect of theinvention is not particularly critical but is preferably 0.001 to 0.03μm. If it is less than 0.001 μm, the antifouling property may not besufficient. Any layer thickness beyond 0.03 μm may be too great forpractical utility.

The glass products, resin products, metal products, ceramic products,etc., which are constituted by the second aspect of the invention, canbe used as parts or members which are liable to be contaminated.

The following is a partial list of such parts and members:

Household electrical appliance parts such as fan blades, electronicrange doors, refrigerator panels, etc.; office equipment parts such ascopying machine contact glass, OHP body mirror, OHP sheet, keyboard,telephone receiver, desk top, etc.; home appliances and furniture suchas glasses, cupboard door, looking glass, window panes, lamp shades,chandeliers, etc.; building materials such as show window, telephonebox, and water tank glass members; vehicle parts such as rolling stockglass, coated surfaces of vehicle bodies, etc.; personal articles suchas spectacle frames, swimming goggle glass, goggles, helmets, clockfaceglass, etc.; amusement equipment parts and products such as pinballmachine glass panels, playing cards, mahjong tiles, etc.; coatedsurfaces of furniture and pianos;

Personal accessories such as tie pins, necklaces, pierce-type ear-rings,etc.; metal or metal-plated members such as faucets, brasswind andwoodwind instruments, golf clubs, door handles, dumbbells, cutters,etc.; ceramic products such as insulators, tiles, toilet fixtures,tableware, roofing tiles, etc.; stone products such as tombstones, gostones, marbles, etc.; paper products such as wallpaper, screen-doorpaper, books, posters, photographs, etc.; and leather goods such aswallets, boots and shoes, bags, wristwatch bands, baseball gloves, etc.

The third aspect of the present invention is now described in detail.

The surface-treating method according to the third aspect of theinvention comprises coating a substrate surface with a treating solutioncomprising (1) a silicon-containing organic fluoropolymer of the abovegeneral formula (Ix), which has been explained in the description of thesecond aspect of the invention, (2) a fluorine-containing organicsolvent and (3) a silane compound.

The first component of the above treating solution is asilicon-containing organic fluoropolymer (1) of the above generalformula (Ix). The n_(x) in said general formula (Ix) represents aninteger of 1 or above. There is no upper limit on the value of the n_(x)but it preferably represents an integer between 1 and 10, in order thatthe object of the third aspect of the invention may be accomplished.

In the third aspect of the invention, said silicon-containing organicfluoropolymer (1) may be a mixture of the polymers of the above generalformula (Ix). When the silicon-containing organic fluoropolymer existsas a mixture, the n_(x) can be expressed in mean. The mean value of then_(x) is preferably from 1.3 to 3 and more preferably 1.5 to 2.5, inconsideration of the object of the third aspect of the invention.

The number average molecular weight of said silicon-containing organicfluoropolymer (1) is preferably from 5×10² to 1×10⁵. If it is less than5×10², the desired effect of the third aspect of the invention may notbe expressed. On the other hand, if it exceeds 1×10⁵, processability maybe adversely affected. The more preferred range is from 1×10³ to 1×10⁴.

The second component of the treating solution for use in thesurface-treating method according to the third aspect of the inventionis a fluorine-containing organic solvent (2).

This fluorine-containing organic solvent (2) is not particularlycritical in kind but includes perfluorohexane,perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, andHCFC225, among other solvents. Particularly preferred is HCFC225 inwhich said silicon-containing organic fluoropolymer (1) is easilysoluble and which is readily available.

The third component of the treating solution for use in thesurface-treating method according to the third aspect of the inventionis a silane compound (3).

This silane compound (3) is not so critical in kind, although saidsilicon-containing organic fluoropolymer (1) is excluded. Thus, therecan be mentioned silicon alkoxides represented by the following generalformula (III);

Si(OR¹¹)₄  (III)

wherein R¹¹ represents an aliphatic hydrocarbon group, the carbon numberof which being not particularly limited; and partially hydrolyzedcondensation products of the compounds of the above general formula(III). Among them, tetraethoxysilane is particularly preferred in viewof its availability.

The proportion of the above respective components (1), (2) and (3),which are constituting the treating solution in use for thesurface-treatment method according to the third aspect of the invention,is not particularly restricted but the (1):(2) ratio is preferably from1:1 to 1:10000 by weight. If the proportion of (1) is too large, theviscosity will be increased so much as to interfere with handling. If itis too small, the antifouling effect will not be sufficient. The morepreferred ratio is from 1:4 to 1:1000. On the other hand, the (1):(3)ratio is preferably in the range of from 10:1 to 1:100 by weight. If theproportion of (1) is too large, no sufficient improvement will berealized in weatherability. If it is too small, the antifouling effectwill not be sufficient. The more preferred range is from 5:1 to 1:10.

To the treating solution of the third aspect of the present inventioncan be added in use finely divided powders of a filler, e.g. silica,alumina, titanium dioxide, carbon, cement, etc.; finely divided powdersof an alkoxide of titanium, aluminum, or the like; or finely dividedpowders of a fluororesin, e.g. low-molecular-weightpolytetrafluoro-ethylene, tetrafluoroethylene-hexafluoropropylenecopolymer, etc., as a hardness regulator or extender. In addition, thenecessary hardness regulation be achieved by adding a conventionalcrosslinking agent or a cure catalyst, such as water, hydrochloric acid,sulfuric acid, carboxylic acids and sulfonic acids.

In applying said treating solution according to the third aspect of theinvention, the substrate surface can be coated with said treatingsolution. The coating technique includes but is not limited to brushcoating, spray coating, spin coating, dip coating, roll coating, gravurecoating and curtain flow coating.

There is no particular limitation on the thickness of the layer, whichis formed from the treating solution in the surface-treating methodaccording to the third aspect of the invention. The thickness is,however, preferably in the range of from 0.001 to 0.03 μm. If it is lessthan 0.01 μm, the antifouling effect will be insufficient. Conversely ifthe thickness exceeds 0.03 μm, the layer will rather interfere with theproduct function.

The surface-treating method according to the third aspect of theinvention includes, in addition to the above-described method, thefollowing method;

An under-layer, which is formed on the substrate surface from a treatingsolution (N) comprising the silane compound [excluding thesilicon-containing organic fluoropolymer (1)] (3), is coated with atreating solution (M) comprising said silicon-containing organicfluoropolymer (1) of the general formula (Ix) and thefluorine-containing organic solvent (2).

The silane compound (3) is diluted with an organic solvent, e.g. methylalcohol, ethyl alcohol, isopropyl alcohol, ethyl acetate, acetone, etc.;or water to prepare said treating solution (N) with a specificconcentration. This concentration is not so critical but is preferablywithin the range of from 2 to 80% by weight. If it is less than 2% byweight, it will take a long time for a silica sol to be formed, whilethe use of a concentration in excess of 80% by weight will cause anexcessive viscosity build-up to sacrifice workability.

To said treating solution (N) is added a conventional catalyst, e.g.hydrochloric acid, and the mixture is allowed to stand to give a silicasol. The sol is then diluted with said solvent to a concentrationsuitable for coating. There is no particular limitation on standing timebut it may for example be 2 to 10 days. The concentration after dilutionis dependent upon the desired thickness of the under-layer but may forexample be 0.2 to 2% by weight.

Next, the substrate surface is coated with the diluted treating solution(N). Th coating technology used includes but is not limited to brushcoating, spray coating, spin coating, dip coating, roll coating, gravurecoating and curtain flow coating. By the above procedure, a silanolpolymer gel layer is formed on the substrate surface.

The coated substrate is then heated, whereby an under-layer composedpredominantly of silicon oxide is obtained. The necessary heatingtemperature varies with kinds of the substrate but may for example befrom 100 to 300° C. There is no particular limitation on heating time,although it may for example be in the range of 10 minutes to 3 hours.The thickness of the under-layer formed is not particularly critical,either, but is generally within the range of from 0.05 to 0.1 μm.

Thereafter, the under-layer constructed as above on the substratesurface is coated with the treating solution (M). The coating technologyused for this purpose includes brush coating, spray coating, spincoating, dip coating, roll coating, gravure coating and curtain flowcoating, among other techniques.

The thickness of the layer formed from said treating solution (M) is notparticularly critical but is preferably from 0.001 to 0.03 μm. If it isless than 0.001 μm, the antifouling effect will not be sufficient. Anythickness beyond 0.03 μm will be too great for practical utility.

The substrate to which the surface-treating method of the third aspectof the invention can be applied with advantage includes those membersthat are liable to be contaminated in use.

The following is a partial list of such members:

Personal accessories such as tie pins, necklaces, pierce-type earrings,etc.; metal or metal-plated members such as faucets, brasswind andwoodwind instruments, golf clubs, door handles, dumbbells, cutters,etc.; ceramic products such as insulators, floor tiles, toilet fixtures,tableware, roofing tiles, etc.; stone products such as tombstones, gostones, marbles, etc.; paper products such as wallpaper, screen-doorpaper, books, posters, photographs, etc.; leather goods such as wallets,boots and shoes, bags, wristwatch bands, baseball gloves, etc.

Household electrical appliance parts such as fan blades, electronicrange door, refrigerator panel, etc.: office equipment parts such ascopying machine contact glass, OHP body mirror, OHP sheet, keyboards,telephone receivers, desks, etc.; home utensils and furniture such asglasses, cupboard door, looking glass, window panes, lamp shades,chandeliers, etc.; building materials such as show window, telephonebox, and water tank glass members; vehicle parts such as rolling stockglass, coated surfaces of vehicle bodies, etc.; personal articles suchas spectacle frame, swimming goggle glass, goggles, helmet, clockfaceglass, etc.; amusement equipment parts and products such as pinballmachine glass panels, playing cards, mahjong tiles, etc.; coatedsurfaces of furniture and pianos.

The surface-treating method according to the third aspect of theinvention is characterized in that the antifouling effect islong-lasting and the treated substrates have sufficient weatherability,so that the following substrates, among the above-mentioned substrates,are particularly suited.

Door handles; ceramic materials such as roofing tiles; stone productssuch as tombstones, go stones, and marbles; copying machine contactglass; window panes; vehicle parts such as rolling stock glass andcoated surfaces of vehicles; and amusement products and goods such aspinball machine glass panels, playing cards, mahjong tiles, and so on.

The fourth aspect of the present invention is now described in detail.

The surface-treating composition according to the fourth aspect of theinvention comprises (1) a silicon-containing organic fluoropolymer ofthe general formula (Ix) described hereinbefore in connection with thesecond aspect of the invention, (2) a fluorine-containing organicsolvent and (4) an organic solvent [excluding the fluorine-containingorganic solvent (2)].

The first component of the surface-treating composition according to thefourth aspect of the invention is a silicon-containing organicfluoropolymer (1) of the general formula (Ix). The n_(x) in the generalformula (Ix) represents an integer of 1 or above. There is no upperlimit to the value of the n_(x) but it is preferably an integer between1 and 10, in order to accomplish the object of the fourth aspect of theinvention.

In the fourth aspect of the invention, said silicon-containing organicfluoropolymer (1) may be a mixture of the polymers of the generalformula (Ix). When said silicon-containing organic fluoropolymer existsas such a mixture, the n_(x) can be expressed in mean. The mean value ofthe n_(x) is preferably from 1.3 to 3 and more preferably from 1.5 to2.5 in view of the object of the fourth aspect of the invention.

The number average molecular weight of said silicon-containing organicfluoropolymer (1) is preferably from 5×10² to 1×10⁵. If it is less than5×10², the objective effect of the fourth aspect of the invention willnot be expressed. If it exceeds 1×10⁵, processability will be adverselyaffected. The more preferred molecular weight range is from 1×10³ to1×10⁴.

The second component of the surface-treating composition according tothe fourth aspect of the invention is a fluorine-containing organicsolvent (2).

The fluorine-containing organic solvent (2) is not particularly limitedin kind but includes the species mentioned for the the third aspect ofthe present invention, among others. Particularly preferred is HCFC225in which said silicon-containing organic fluoropolymer (1) is easilysoluble and which is readily available.

The third component of the surface-treating composition according to thefourth aspect of the invention is an organic solvent (4) [exclusive ofsaid fluorine-containing organic solvent (2)]. This organic solvent (4)is not particularly limited in kind but includes alcohols, ketones,esters, and halogenated (exclusive of fluorinated) hydrocarbons, amongothers. Particularly preferred are alcohols.

Said alcohols are not particularly limited in kind but includesmonohydric alcohols containing 1 to 8 carbon atoms and polyhydricalcohols such as ethylene glycol, glycerol, etc., for example. Amongthem, preferred are monohydric alcohols containing 1 to 4 carbon atomsand more preferred are isopropyl alcohol because those alcohols arereadily available and good solvents for said silicon-containing organicfluoropolymer (1).

Among the respective components of the surface-treating compositionaccording to the fourth aspect of the invention, both thefluorine-containing organic solvent (2) and the organic solvent (4)serve as solvents for the silicon-containing organic fluoropolymer (1).Between the fluorine-containing organic solvent (2) and the organicsolvent (4), the fluorine-containing organic solvent (2) iscomparatively more expensive and the organic solvent (4) is generallyless expensive. Therefore, the surface-treating composition of thefourth aspect of the invention can be provided at a relatively low costby increasing the proportion of the organic solvent (4) to thefluorine-containing organic solvent (2).

In the surface-treating composition according to the fourth aspect ofthe present invention, the proportion of the fluorine-containing organicsolvent (2) to the organic solvent (4) is preferably within the range of(2):(4)=1:99 to 99:1 by weight. If the proportion of thefluorine-containing organic solvent (2) is smaller than 1% by weight,the solubility of the silicon-containing organic fluoropolymer (1) willbe so low that the desired function of the surface-treating compositionmay not be expressed. On the other hand, if the limit of 99% by weightis exceeded, the production cost of the surface-treating composition ofthe invention may not be reasonably controlled. The more preferred ratiois from 1:99 to 50:50.

To the surface-treating composition of the fourth aspect of theinvention can be added in use finely divided powders of a filler, e.g.silica, alumina, titanium dioxide, carbon, cement, etc.; finely dividedpowders of an alkoxide of titanium, aluminum, silicon, or the like; orfinely divided powders of a fluororesin, e.g. low-molecular-weightpolytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylenecopolymer, etc., as a hardness regulator or extender. In addition, thenecessary hardness regulation can be achieved by adding a conventionalcrosslinking agent or a cure catalyst, such as water, hydrochloric acid,sulfuric acid, carboxylic acids and sulfonic acids.

In applying the surface-treating composition according to the fourthaspect of the invention, the substrate surface can be coated with saidsurface-treating composition. The coating technology used is notparticularly limited but typically includes the various techniquesmentioned for the third aspect of the invention.

The fourth aspect of the invention can also be carried into practice bycoating an under-layer, which is formed in advance on the substratesurface from a treating solution comprising a silane compound, with asolvent dilution of said silicon-containing organic fluoropolymer.

Said silane compound is not particularly limited in kind but typicallyincludes the compound (3) mentioned for the third aspect of the presentinvention, although tetraethoxysilane is particularly preferred in viewof its availability.

The silane compound is diluted with an organic solvent, e.g. methylalcohol, ethyl alcohol, isopropyl alcohol, ethyl acetate, acetone, etc.;or water to prepare a solution with a specific concentration. Thisconcentration is not so critical but is preferably within the range of 2to 80% by weight. If it is less than 2% by weight, it will take a longtime for a silica sol to be formed, while the use of a concentration inexcess of 80% by weight will cause an excessive viscosity build-up tosacrifice workability.

To the above solution is added a conventional catalyst, e.g.hydrochloric acid, and the mixture is allowed to stand to give a silicasol. The sol is then diluted with said solvent to a concentrationsuitable for coating. There is no particular limitation on standing timebut it may for example be 2 to 10 days. The concentration after dilutionis dependent upon the desired thickness of the under-layer and may forexample be from 0.2 to 2% by weight.

Next, the substrate surface is coated with the above diluted solution.The coating technology used is not particularly limited but includes thevarious techniques mentioned for the third aspect of the presentinvention. By the above procedure, a silanol polymer gel layer is formedon the substrate surface.

The coated substrate is then heated, whereby an under-layer composedpredominantly of silicon oxide is obtained. The necessary heatingtemperature varies with kinds of the substrates but may for example befrom 100 to 300° C. There is no particular limitation on heating time,although it may for example be in the range of 10 minutes to 3 hours.The thickness of the under-layer is not particularly critical, but isgenerally within the range of from 0.05 to 0.1 μm.

Thereafter, the under-layer constructed as above on the substratesurface is coated with said solvent dilution of the silicon-containingorganic fluoropolymer. The coating technology used for this purpose isnot particularly limited but includes the techniques mentioned for thethird aspect of the present invention.

The thickness of the layer formed from the surface-treating compositionof the fourth aspect of the invention is not particularly critical butis preferably from 0.001 to 0.03 μm. If it is less than 0.001 μm, theantifouling effect will not be sufficient. Any thickness beyond 0.03 μmwill be too great for practical utility.

The substrate to which the surface-treating method according to thefourth aspect of the invention can be applied with advantage includesthose members that are liable to be contaminated in use.

The following is a partial list of such members:

Personal accessories such as tie pins, necklaces, pierce-type earrings,etc.; metal or metal-plated products and members such as faucets,brasswind and woodwind instruments, golf clubs, door handles, dumbbells,cutters, etc.; ceramic products such as insulators, floor tiles, toiletfixtures, tableware, roofing tiles, etc.; stone products such astombstones, go stones, marbles, etc.; paper products such as wallpaper,screen-door paper, books, posters, photographs, etc.; leather goods suchas wallets, boots and shoes, bags, wrist-watch bands, baseball gloves,etc.;

Household electrical appliance parts such as fan blades, electronicrange door, refrigerator panel, etc.; office equipment parts such ascopying machine contact glass, OHP body mirror, OHP sheet, keyboards,telephone receivers, desks, etc.; home utensils and furniture such asglasses, cupboard door, looking glass, window panes, lamp shades,chandeliers, etc.; building materials such as show window, telephonebox, and water tank glass members; vehicle parts such as rolling stockglass, coated surfaces of vehicle bodies, etc.; personal articles suchas spectacle frames, swimming goggle glass, goggles, helmet, clockfaceglass, etc.; amusement equipment parts and products such as pinballmachine glass panels, playing cards, mahjong tiles, etc.; coatedsurfaces of furniture and pianos.

The surface-treating method according to the fourth aspect of theinvention is characterized in that the antifouling effect islong-lasting and that the surface-treating composition used can beeasily prepared. In this respect, the surface-treating method accordingto the fourth aspect of the invention can be applied with particularadvantage to the following substrates among the above-listed substrates.

Home ware and members such as glasses, cupboard door, looking glass,window panes, lamp shades, chandeliers, etc.; building components andmembers such as show window, telephone booth, and water tank glass; andvehicle members and parts such as rolling stock glass and coatedsurfaces of vehicle bodies.

The fifth aspect of the present invention is now described in detail.

The anti-icing agent according to the fifth aspect of the inventioncomprises a silicon-containing organic fluoropolymer of the generalformula (Ix) described hereinbefore in connection with the second aspectof the present invention.

In the above general formula (Ix), the n_(x) represents an integer of 1or above. There is no particular upper limit to the value of the n_(x);however, it is preferably an integer of 1 to 10 in order to achieve theobject of the fifth aspect of the invention.

The silicon-containing organic fluoropolymer (1) in the fifth aspect ofthe invention may be a mixture of the polymers of the above generalformula (Ix). When the silicon-containing organic fluoropolymer existsas a mixture, the n_(x) can be expressed in mean. The mean value of then_(x) is preferably from 1.3 to 3 and more preferably from 1.5 to 2.5 inconsideration of the object of the fifth aspect of the invention.

The preferred number average molecular weight of said silicon-containingorganic fluoropolymer (1) is from 5×10² to 1×10⁵. If it is less than5×10², the desired effect of the fifth aspect of the invention may notbe expressed. On the other hand, if the upper limit of 1×10⁵ isexceeded, processability will be adversely affected. The more preferredrange is from 1×10³ to 1×10⁴.

To the anti-icing agent of the fifth aspect of the invention can beadded finely divided powders of a filler, e.g. silica, alumina, titaniumdioxide, carbon, cement, etc.; finely divided powders of an alkoxide oftitanium, aluminum, silicon, or the like; ao finely divided powders of afluororesin, e.g. low-molecular-weight polytetrafluoroethylene,tetrafluoroethylene-hexafluoropropylene copolymer, etc., as a hardnessregulator or extender. In addition, the necessary hardness can be soughtby adding a conventional crosslinking agent or cure catalyst, such aswater, hydrochloric acid, sulfuric acid, carboxylic acids and sulfonicacids.

In applying the anti-icing agent the fifth aspect of the invention, thesubstrate surface can be coated with said silicon-containing organicfluoropolymer. The coating technology used here is not particularlylimited but typically includes the various techniques mentioned for thethird aspect of the invention.

Dilution of the polymer with a solvent beforehand makes coating easier.There is no particular limitation on types of the solvent used for thispurpose. For example, perfluorohexane, perfluoromethylcyclohexane,perfluoro-1,3-dimethylcyclohexane, HCFC225, etc. can be mentioned.

The fifth aspect of the invention can also be carried into practice bycoating an under-layer, which is formed in advance on the surfacesubstrate from a treating solution comprising a silane compound, with asolvent dilution of said silicon-containing organic fluoropolymer.

Said silane compound is not particularly limited in kind but typicallyincludes the silane compounds (3) mentioned hereinbefore in connectionwith the third aspect of the present invention, althoughtetraethoxysilane is particularly preferred in view of its availability.

Said silane compound is diluted with an organic solvent, e.g. methylalcohol, ethyl alcohol, isopropyl alcohol, ethyl acetate, acetone, etc.;or water to prepare a solution with a specific concentration. Thisconcentration is not so critical but is preferably within the range of 2to 80% by weight. If it is less than 2% by weight, it will take a longtime for a silica sol to form, while the use of a concentration inexcess of 80% by weight will cause an excessive viscosity build-up tosacrifice workability.

To the above solution is added a conventional catalyst, e.g.hydrochloric acid, and the mixture is allowed to stand so as to give asilica sol. The sol is then diluted with said solvent to a concentrationsuitable for coating. There is no particular limitation on standing timebut it may for example be from 2 to 10 days. The concentration afterdilution is dependent upon the desired thickness of the under-layer butmay for example be from 0.2 to 2% by weight.

Next, the substrate surface is coated with said diluted solution. Thecoating technology used is not particularly limited but includes thevarious techniques mentioned for the third aspect of the presentinvention. By the above procedure, a silanol polymer gel layer is formedon the substrate surface.

The coated substrate is then heated, whereby an under-layer composedpredominantly of silicon oxide is obtained. The necessary heatingtemperature varies with kinds of the substrate but may for example befrom 100 to 300° C. There is no particular limitation on heating time,although it may for example be in the range of 10 minutes to 3 hours.The thickness of the under-layer formed is not particularly critical,either, but is generally within the range of from 0.05 to 0.1 μm.

Thereafter, the under-layer constructed as above on the substratesurface is coated with said solvent dilution of the silicon-containingorganic fluoropolymer. The coating technology used for this purpose isnot particularly limited but includes the techniques mentioned for thethird aspect of the present invention.

The thickness of the silicon-containing organic fluoropolymer layerformed from the anti-icing agent of the fifth aspect of the invention isnot particularly critical but is preferably from 0.001 to 0.03 μm. If itis less than 0.001 μm, the anti-icing effect will not be sufficient. Anythickness beyond 0.03 μm will be too great for practical utility.

The substrate to which the anti-icing agent of the fifth aspect of theinvention can be applied with advantage is not particularly limited inkind but includes the members and parts of mobile structures such ascars and rolling stock, aircraft, ships, etc., home and other buildingmembers, special equipment for freeze-point experiments, and householdelectrical appliances such as refrigerators. Particularly, thewindshield glass for cars, airplanes, ships, etc. is an importantsubstrate, for its ice-up may cause an accident.

The sixth aspect of the present invention is now described in detail.

The water-repellent glass member according to the sixth aspect of thepresent invention comprises a glass substrate and, as formed on theglass surface, a layer of a silicon-containing organic fluoropolymer(Ix) described for the second aspect of the invention.

The n_(x) in the above general formula (Ix) represents an integer of 1or above. There is no upper limit to the value of the n_(x) but itpreferably represents an integer between 1 and 10 in order to achievethe object of the invention.

The silicon-containing organic fluoropolymer (1) in the sixth aspect ofthe invention may be a mixture of the polymers of the above generalformula (Ix). When the silicon-containing organic fluoropolymer existsas a mixture, the n_(x) can be expressed in mean. The mean value of then_(x) is preferably from 1.3 to 3 and more preferably from 1.5 to 2.5 inconsideration of the object of the sixth aspect of the invention.

The preferred number average molecular weight of said silicon-containingorganic fluoropolymer (1) is from 5×10² to 1×10⁵. If it is less than5×10², the desired effect of the sixth aspect of the invention may notbe expressed. On the other hand, if the upper limit of 1×10⁵ isexceeded, processability will be adversely affected. The more preferredrange is from 1×10³ to 1×10⁴.

To the silicon-containing organic fluoropolymer can be added in usefinely divided powders of a filler, e.g. silica, alumina, titaniumdioxide, carbon, cement, etc.; finely divided powders of an alkoxide oftitanium, aluminum, silicon, or the like; or finely divided powders of afluororesin, e.g. low-molecular-weight polytetrafluoroethylene,tetrafluoroethylene-hexafluoropropylene copolymer, etc., as a hardnessregulator or extender. In addition, the hardness regulation can beachieved by adding a conventional crosslinking agent or cure catalyst,such as water, hydrochloric acid, sulfuric acid, carboxylic acids andsulfonic acids.

The glass surface can be coated with the silicon-containing organicfluoropolymer in order to form a layer of said silicon-containingorganic fluoropolymer. The coating technology used here is notparticularly limited but typically includes the various techniquesmentioned for the third aspect of the invention.

Dilution of the polymer with a solvent makes coating easier. There is noparticular limitation on the type of solvent used for this purpose. Forexample, the solvents mentioned for the third aspect of the inventioncan be employed.

The sixth aspect of the invention can also be carried into practice bycoating an under-layer, which is formed in advance on the substratesurface from a treating solution of a silane compound, with a solventdilution of said silicon-containing organic fluoropolymer.

Said silane compound is not particularly limited in kind but typicallyincludes the silane compounds (3) mentioned for the third aspect of theinvention, although tetraethoxysilane is particularly preferred in viewof its availability.

The silane compound is diluted with an organic solvent, e.g. methylalcohol, ethyl alcohol, isopropyl alcohol, ethyl acetate, acetone, etc.;or water to prepare a solution with a specific concentration. Thisconcentration is not so critical but is preferably within the range of 2to 80% by weight. If it is less than 2% by weight, it will take a longtime for a silica sol to form, while the use of a concentration inexcess of 80% by weight will cause an excessive viscosity build-up tosacrifice workability.

To the above solution is added a conventional catalyst, e.g.hydrochloric acid, and the mixture is allowed to stand to give a silicasol. The sol is then diluted with said solvent to a concentrationsuitable for coating. There is no particular limitation on standing timebut it may for example be from 2 to 10 days. The concentration afterdilution is dependent upon the desired thickness of the under-layer butmay for example be from 0.2 to 2% by weight.

Next, the substrate surface is coated with said diluted solution. Thecoating technology used is not particularly limited but includes thevarious techniques mentioned for the third aspect of the presentinvention. By the above procedure, a silanol polymer gel layer is formedon the substrate surface.

The coated substrate is then heated, whereby an under-layer composedpredominantly of silicon oxide is obtained. The necessary heatingtemperature varies with kinds of the substrate but generally may forexample be from 100 to 300° C. There is no particular limitation onheating time, although it may for example be in the range of 10 minutesto 3 hours. The thickness of the under-layer formed is not particularlycritical, either, but is generally within the range of from 0.05 to 0.1μm.

Thereafter, the under-layer constructed as above on the substratesurface is coated with said solvent dilution of the silicon-containingorganic fluoropolymer. The coating technology used for this purpose isnot particularly limited, either, but includes the techniques mentionedfor the third aspect of the present invention.

The thickness of the silicon-containing organic fluoropolymer layerformed for the water-repellent glass member according to the sixthaspect of the invention is not particularly critical but is preferablyfrom 0.001 to 0.03 μm. If it is less than 0.001 μm, the water-repellenteffect will not be sufficient. Any thickness beyond 0.03 μm will be toogreat for practical utility.

BEST MODE FOR CARRYING OUT THE INVENTION

The following examples and comparative examples are intended toillustrate the present invention in further detail and should by nomeans be construed as defining the scope of the invention.

SYNTHESIS EXAMPLE 1

A four-necked 2.0-L flask equipped with a stirrer, drip funnel, refluxcondenser and thermometer was charged with 2617 g (10.3 mole) of iodine,213.2 g (1.54 mole) of potassium carbonate and 9,000 g ofhexachloro-1,3-butadiene. In a nitrogen steam, 4,000 g (1.03 mole) ofω-fluoropolyperfluorooxetaneacyl fluoride of the chemical formulaF—(CF₂CF₂CF₂O)_(n)—CF₂CF₂COF (average molecular weight of 3,900) wasadded dropwise at a rate of 10 mL/min. with maintaining at a systemtemperature of 160° C.

After completion of dropwise addition, the reaction temperature wasincreased to 185° C. and the reaction was carried out for 20 hours.

After completion of the reaction, the system was cooled down and thepotassium salt was filtered off. Then, the bottom layer of the liquidphase was separated using a separately funnel. This layer was washedwith several portions of acetone and dissolved in 1 L ofperfluorohexane, and the fine insoluble matter was filtered off using aglass filter. The filtrate was distilled under a reduced pressure toremove the volatile matter thoroughly to thereby recover 3,890 g (95%yield) of ω-fluoropolyperfluorooxetane iodide of the chemical formulaF—(CF₂CF₂CF₂O)_(n)—CF₂CF₂I.

Infrared spectrophotometry revealed complete disappearance of theabsorption of —C(═O)F at 1890 cm⁻¹ and a new absorption of —CF²I at 910cm⁻¹.

SYNTHESIS EXAMPLE 2

A four-necked 200-mL flask equipped with a stirrer, drip funnel, refluxcondenser and thermometer was charged with a solution of 40 g ofω-fluoropolyperfluorooxetane iodide of the chemical formulaF—(CF₂CF₂CF₂O)_(n)—CF₂CF₂I as synthesized in Synthesis Example 1 in 80 gof hexafluorotetrachlorobutane [Daiflon Solvent S-316 (manufactured byDaikin Kogyo)] and 1.5 g (1×10⁻² mole) of di-t-butyl peroxide. Theatmosphere of the system was thoroughly purged with nitrogen gas. Then,16.1 g (0.10 mole) of vinyltrichlorosilane was added dropwise using thedrip funnel in a nitrogen stream. After completion of dropwise addition,the system temperature was increased to 120° C. and the reaction wascarried out for 4 hours. After completion of the reaction, the volatilefraction was completely distilled off under a reduced pressure toprovide 38.7 g (90% yield) of iodine-terminated silicon-containingorganic fluoropolymer (A).

SYNTHESIS EXAMPLE 3

A four-necked 200-mL flask equipped with a stirrer, drip funnel, refluxcondenser and thermometer was charged with a solution of 34.4 g (8×10⁻³mole) of the silicon-containing organic fluoropolymer (A) synthesized inSynthesis Example 2 in 50 g of perfluorohexane, and 2.1 g (3.2×10⁻²mole) of zinc was dispersed with intense stirring. After the system wascooled on an ice-water bath, 10 g of anhydrous methanol was addeddropwise in a nitrogen stream.

After completion of dropwise addition, the ice-water bath was removedand the reaction was carried out under reflux for 2 hours. The insolublematter was then filtered off and the bottom layer of the liquid phasewas separated using a separatory funnel. This solution was washed with 3portions of anhydrous methanol and distilled under a reduced pressure toremove the volatile fraction thoroughly. As a result, 31.6 g (92% yield)of a hydrogen-terminated silicon-containing organic fluoropolymer (B)was obtained.

¹H-NMR analysis revealed a broad signal assignable to the hydrogen atomsindicated in the following formula at 1.2 to 3.0 ppm. As measured with5.0 mole % of ω-fluoroperfluorooxetane hydride added as an internalstandard and calculated by means of the following computation formula,the degree of polymerization was 2.0.

I/I_(s)=[0.95(3P+1)]/0.05

I: integral absorption intensity at 1.2 to 3.0 ppm

I_(s): integral absorption intensity of internal standard

P: degree of polymerization

SYNTHESIS EXAMPLE 4

The procedure of Synthesis Example 2 was repeated except that di-t-butylperoxide was used in a proportion of 0.29 g (2×10⁻³ mole) to provide asilicon-containing organic fluoropolymer (C).

SYNTHESIS EXAMPLE 5

Using the silicon-containing organic fluoropolymer (C), the procedure ofSynthesis Example 3 was otherwise repeated. The degree of polymerizationof the resulting silicon-containing organic fluoropolymer (D) asdetermined in the same manner as in Synthesis Example 3 was 1.0.

EXAMPLE 1 AND COMPARATIVE EXAMPLES 1 AND 2

The polymers obtained in Synthesis Examples 3 and 5 and the commercialfluorine-containing silane coupling agent KBM7803 [C₈F₁₇CH₂CH₂Si(OCH₃)₃,manufactured by Shin-Etsu Chemical] (hereinafter referred to briefly asthe commercial product) were respectively dissolved in perfluorohexaneto provide treating solutions with 0.1% by weight concentrations.Meanwhile, substrate glass sheets were rinsed with water and, then,washed thoroughly with methanol and acetone. The glass sheets thusprepared were dipped in the treating solutions for 10 seconds, raised,and air-dried for 60 minutes. Then, the sheets were subjected to sonicwashing in perfluorohexane for 5 minutes to eliminate the excessmolecules of the treating solutions and, then, air-dried for use inevaluations.

The evaluations were made by the following methods.

(1) Fingerprint Receptivity:

A fingerprint was taken on each sample and the ease of fingerprinttaking was visually evaluated.

◯: The fingerprint can hardly be taken and the impression formed is notconspicuous.

X: The fingerprint taken is comparable to that on the untreated glasssheet.

Δ: Equivocal

(2) Fingerprint Erasability:

The surface of the sample used for the evaluation of fingerprintreceptivity was wiped with Kimwipe (Jujo-Kimberley) in one reciprocationand the ease of erasing the fingerprint was visually evaluated.

◯: The fingerprint can be completely wiped off.

Δ: Traces of the fingerprint remain after wiping.

X: Traces of the fingerprint spread upon wiping and cannot be easilyremoved.

(3) The Contact Angle for Water was Measured by Sessile Drop Method witha Contact Angle Microscope (CA-DT, Manufactured by Kyowa InterfaceScientific Instruments).

The results of the respective evaluations are shown in Table 1.

TABLE 1 Finger- Finger- Contact Sample for print print angle evaluationreceptivity erasability for water Example 1 Synthesis ◯ ◯ 113° Example 3Comparative Synthesis Δ ◯ 110° Example 1 Example 5 ComparativeCommercial Δ X 110° Example 2 product

EXAMPLE 2 AND COMPARATIVE EXAMPLE 3

The polymer obtained in Synthesis Example 3 and the commercial productwere respectively dissolved in perfluorohexane to prepare treatingsolutions with 0.1% by weight concentrations. Aluminum sheets [0.5 mm,as specified in JIS H4000 (A1050P)] as substrates were rinsed with waterand then washed well with methanol and acetone. The aluminum sheets thusprepared were dipped in the treating solutions, raised, and air-driedfor 60 minutes. The sheets were then subjected to sonic washing inperfluorohexane for 5 minutes to remove the excess molecules of thetreating solutions and air-dried for use in evaluations.

COMPARATIVE EXAMPLE 4

Separately, untreated aluminum sheets were provided.

Evaluations were made according to the following criteria.

The surface of each sample was repeatedly wiped with a hand-held Kimwipe(Jujo-Kimberley) with a medium degree of force in 100 reciprocations.The contact angle for water before wiping and the contact angle forwater after completion of wiping were respectively measured. The contactangles for water was measured by sessile drop method with a contactangle microscope (CA-DT, Kyowa Interface Scientific Instruments).

The results of evaluations are shown in Table 2.

TABLE 2 Contact angle Contact angle Sample for for water for waterevaluation before wiping after wiping Example 2 Synthesis 114° 108°Example 3 Comparative Commercial 111°  98° Example 3 product ComparativeUntreated  88° — Example 4 sheet

EXAMPLE 4

A treating solution was prepared by mixing 0.1% by weight ofsilicon-containing organic fluoropolymer (B) synthesized in SynthesisExample 3 with 99.8% by weight of HCFC225 and 0.1% by weight oftetraethoxysilane.

A glass sheet was washed with water and then washed thoroughly withmethanol and acetone. The glass sheets thus prepared were dipped in theabove treating solution for 1 minute, raised, and allowed to stand at60° C. and 80% RH for 60 minutes. The sheets were then washed withHCFC225 well to remove the excess molecules of the treating solution.

The samples thus prepared were subjected to an accelerated weatheringtest in the I-super UV tester (SUV-W13, manufactured by IwasakiElectric) for 161 hours (equivalent to 3.3 years) and the contact anglesfor water were measured before and after the test by sessile drop methodwith a contact angle microscope (CA-DT, Kyowa Interface ScientificInstruments). The results are shown in Table 3.

COMPARATIVE EXAMPLE 5

A treating solution was prepared in the same manner as in Example 3except that 0.1% by weight of the silicon-containing organicfluoropolymer (B) obtained in Synthesis Example 3 was mixed with 99.9%by weight of HCFC225. The treating solution thus prepared was subjectedto the same test as in Example 3. The results are shown in Table 3.

TABLE 3 Contact angle for water Before test After test Example 3 114°109° Comparative 112° 101° Example 5

EXAMPLE 4

A surface-treating composition was prepared by mixing 0.1% by weight ofthe silicon-containing organic fluoropolymer (B) with 99.9% by weight ofa mixture of 10% by weight of HCFC225 and 90% by weight of isopropylalcohol.

Meanwhile, glass sheets were rinsed with water and then washedthoroughly with methanol and acetone. The glass sheets thus preparedwere dipped in the above surface-treating composition for 1 minute,raised, and allowed to stand at 60° C. and 90% RH for 24 hours. Thesheets were then washed well with HCFC225 to remove the excess moleculesof the surface-treating composition.

COMPARATIVE EXAMPLE 6

A surface-treating composition was prepared by mixing 0.1% by weight ofthe silicon-containing organic fluoropolymer (B) with 99.9% by weight ofHCFC225 in otherwise the same manner as in Example 4 and subjected tothe same test as described. The results are shown in Table 4.

TABLE 4 Contact angle for water Example 4 113° Comparative 113° Example6

COMPARATIVE EXAMPLE 7

It was attempted to prepare a surface-treating composition by mixing0.1% by weight of the silicon-containing organic fluoropolymer (B) with99.9% by weight of isopropyl alcohol. However, the two components wereimmiscible, failing to give a useful surface-treating composition.

EXAMPLE 5

The polymer obtained in Synthesis Example 3 was dissolved inperfluorohexane to prepare a treating solution with a 0.1% by weightconcentration. Glass sheets were rinsed with water and then washedthoroughly with methanol and acetone. The glass sheets thus preparedwere dipped in the above treating solution for 10 seconds, raised, andair-dried for 60 minutes. The sheets were then subjected to sonicwashing in perfluorohexane for 5 minutes to remove the excess moleculesof the treating solution and air-dried.

The treated glass sheets were allowed to stand on dry ice in anatmosphere controlled at 20° C. and 70% RH to let a deposit of ice formin a thickness of about 0.2 mm on the glass surface.

The iced surface of each glass sheet was gently rubbed against using apolyethylene spatula in a few reciprocations to remove the deposit ofice to evaluate the anti-icing effect. The following evaluation criteriawere used.

O: The deposit of ice can be easily scraped off to expose the glasssurface completely.

Δ: The glass surface can be exposed but the deposit of ice remainslocally.

X: The glass surface cannot be exposed.

The results are shown in Table 5.

COMPARATIVE EXAMPLE 8

The commercial product was dissolved in perfluorohexane to prepare atreating solution with a 0.1% by weight concentration. Meanwhile, glasssheets were rinsed with water and then washed thoroughly with methanoland acetone. The glass sheets thus prepared were dipped in the abovetreating solution for 10 seconds, raised, and air-dried for 60 minutes.The glass sheets were then subjected to sonic washing in perfluorohexanefor 5 minutes to remove the excess molecules of the treating solutionand air-dried.

The treated glass sheets were allowed to stand on dry ice in anatmosphere controlled at 20° C. and 70% RH to let a deposit of ice formin a thickness of about 0.2 mm on the glass surface.

The anti-icing effect was evaluated just as in Example 5.

The results are shown in Table 5.

COMPARATIVE EXAMPLE 9

Glass sheets, which was rinsed with water and thoroughly washed withmethanol and acetone, were allowed to sit on dry ice in an atmosphere at20° C. and 70% RH to let deposits of ice form in a thickness of about0.2 mm.

The anti-icing effect was evaluated just as in Example 5.

The results are shown in Table 5.

TABLE 5 Sample Evaluation Example 5 Synthesis ◯ Example 3 ComparativeCommercial Δ Example 8 product Comparative — X Example 9

EXAMPLE 6 AND COMPARATIVE EXAMPLE 10

The polymer obtained in Synthesis Example 3 and the commercial productwere respectively dissolved in perfluorohexane to prepare treatingsolutions with 0.1% by weight concentrations. Meanwhile, glass sheetswere rinsed with water and then washed thoroughly with methanol andacetone. The glass sheets thus prepared were dipped in the treatingsolutions for 10 seconds, raised, and air-dried for 60 minutes. Thesheets were then subjected to sonic washing in perfluorohexane for 5minutes to remove the excess molecules of the treating solution andair-dried for use in evaluations.

The contact angle for water and waterdrop tumbling-down angle weremeasured by sessile drop method with a contact angle microscope (CA-DT,Kyowa Interface Scientific Instruments).

The peel strength was measured with a commercial cellophane tape (18 mmwide, manufactured by Sekisui Chemical Co., Ltd.) at a pulling speed of50 mm/second.

TABLE 6 Contact Waterdrop angle tumbling- Peel Sample for water downangle strength Example 6 Synthesis 111° 14° 123 g Example 3 ComparativeCommercial 110° ≧30° 213 g Example 10 product

INDUSTRIAL APPLICABILITY

The fluorine-containing polymer according to the first aspect of thepresent invention, the construction of which has been describedhereinbefore, is very satisfactory in antifouling property, particularlyagainst fingerprint, and contact angle for water, so that it can be usedwith advantage in a broad range of applications such as optical lenses,spectacle lenses, and glass, metal, ceramic, and organic parts ormembers.

The antifouling substrate according to the second aspect of the presentinvention, the construction of which has been described hereinbefore, isvery satisfactory in antifouling property, particularly againstfingerprint, so that is can be used with advantage in the fields ofglass, resin, metal, ceramics, wood, porcelain, stoneware and leather.

The surface-treating method according to the third aspect of the presentinvention, the construction of which has been described hereinbefore,provides a sufficient and lasting antifouling effect as well assufficient weatherability and, as such, can be used with advantage inthe field of products which must be protected against fouling underoutdoor and other rugged conditions.

The surface-treating composition according to the fourth aspect of thepresent invention, the construction of which has been describedhereinbefore, insures a sufficient and long-lasting antifouling effect,as well as high weatherability, and is inexpensive, so that it isparticularly suited for universal use.

The anti-icing agent according to the fifth aspect of the presentinvention, the construction of which has been described hereinbefore, iseffective in preventing deposition of ice and insures ease of removingdeposits of ice.

The water-repellent glass member according to the sixth aspect of thepresent invention, the construction of which has been describedhereinbefore, is outstanding in durability, surface lubricity andsurface antitackiness, besides being highly water-repellent, so that itcan be used with advantage as windshield glass for buildings, cars,ships, and aircraft, among others.

What is claimed is:
 1. A silicon-containing organic fluoropolymerrepresented by the general formula (I), which comprises having a numberaverage molecular weight of from 5×10² to 1×10⁵:

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R² represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; m represents 1, 2 or 3; and nrepresents an integer of 2 or above.
 2. A mixture of silicon-containingorganic fluoropolymers represented by the general formula (Ia) andhaving a number average molecular weight of from 5×10² to 1×10⁵, whereing is 0 or an integer of 1 or above and the mean value of the g isgreater than 1 in said mixture provided said mixture ofsilicon-containing organic fluoropolymers contains a silicon-containingorganic fluoropolymer wherein the g is an integer of 2 or above:

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R² represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; and m represents 1, 2 or 3.3. The silicon-containing organic fluoropolymer according to claim 1,which is a polymer represented by the general formula (II) and having anumber average molecular weight of from 5×10² to 1×10⁵:

wherein p represents an integer of 1 or above; Y represents hydrogen oralkyl containing 1 to 4 carbon atoms; X represents hydrogen, bromo oriodo; R¹ represents hydroxy or a hydrolyzable substituent group; R²represents hydrogen or a monovalent hydrocarbon group; 1 represents 0, 1or 2; m represents 1, 2 or 3; and n represents an integer of 2 or above.4. A mixture of silicon-containing organic fluoropolymers represented bythe general formula (IIa) and having a number average molecular weightof from 5×10² to 1×10⁵, wherein g is 0 or an integer of 1 or above andthe mean value of the g is greater than 1 in said mixture, provided saidmixture of silicon-containing organic fluoropolymers contains asilicon-containing organic fluoropolymer wherein the g is an integer of2 or above:

wherein p represents an integer of 1 or above; Y represents hydrogen oralkyl containing 1 to 4 carbon atoms; X represents hydrogen, bromo oriodo; R¹ represents hydroxy or a hydrolyzable substituent group; R²represents hydrogen or a monovalent hydrocarbon group; 1 represents 0, 1or 2; and m represents 1, 2 or
 3. 5. A process for preparing thesilicon-containing organic fluoropolymer according to claim 1, whichcomprises reacting an iodine-terminated organic fluoropolymerrepresented by the general formula;

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; with avinylsilane compound represented by the general formula:

wherein Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;R¹ represents hydroxy or a hydrolyzable substituent group; R² representshydrogen or a monovalent hydrocarbon group; 1 represents 0, 1 or 2; andm represents 1, 2 or
 3. 6. A process for preparing the mixture ofsilicon-containing organic fluoropolymers according to claim 2, whichcomprises reacting an iodine-terminated organic fluoropolymerrepresented by the general formula;

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; with avinylsilane compound represented by the general formula:

wherein Y represents hydrogen or alkyl containing 1 to 4 carbon atoms;R¹ represents hydroxy or a hydrolyzable substituent group; R² representshydrogen or a monovalent hydrocarbon group; 1 represents 0, 1 or 2; andm represents 1, 2 or
 3. 7. A surface-treating method for a substrate,which comprises coating the substrate surface with a treating solutioncomprising (1) a silicon-containing organic fluoropolymer represented bythe general formula (Ix), (2) a fluorine-containing organic solvent and(3) a silane compound excepting said silicon-containing organicfluoropolymer (1):

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R² represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; m represents 1, 2 or 3; andn_(x) represents an integer of 1 or above.
 8. A surface-treating methodfor a substrate, which comprises coating the substrate surface with atreating solution (N) comprising (3) a silane compound excepting asilicon-containing organic fluoropolymer (1) represented by the generalformula (Ix) for forming an under-layer, and then coating theunder-layer with a treating solution (M) comprising (1) thesilicon-containing organic fluoropolymer and (2) a fluorine-containingorganic solvent:

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R² represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; m represents 1, 2 or 3; andn_(x) represents an integer of 1 or above.
 9. A surface-treatingcomposition which comprises (1) a silicon-containing organicfluoropolymer represented by the general formula (Ix), (2) afluorine-containing organic solvent and (4) an organic solvent exceptingsaid fluorine-containing organic solvent (2):

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R² represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; m represents 1, 2 or 3; andn_(x) represents an integer of 1 or above.
 10. The surface-treatingcomposition according to claim 9, wherein the organic solvent (4)excepting the fluorine-containing organic solvent (2) is alcohols. 11.An anti-icing agent which comprises a silicon-containing organicfluoropolymer represented by the general formula (Ix):

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R² represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; m represents 1, 2 or 3; andn_(x) represents an integer of 1 or above.
 12. A water-repellent glassmember which comprises a glass substrate and, as formed on the glasssurface, a layer of a silicon-containing organic fluoropolymerrepresented by the general formula (Ix), and which is used in vehicles:

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R² represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; m represents 1, 2 or 3; andn_(x) represents an integer of 1 or above.
 13. An antifouling substratewhich comprises a substrate and, as formed on the surface thereof, alayer of a silicon-containing organic fluoropolymer represented by thegeneral formula (Ix) and having a number average molecular weight offrom 5×10² to 1×10⁵:

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R² represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; m represents 1, 2 or 3; andn_(x) represents an integer of 2 or above.
 14. A process for preparingan antifouling substrate, which comprises coating the substrate surfacewith a treating solution comprising a mixture of silicon-containingorganic fluoropolymers represented by the general formula (Ia) andhaving a number average molecular weight of from 5×10² to 1×10⁵, whereing is 0 or an integer of 1 or above and the mean value of the g isgreater than 1 in said mixture provided said mixture ofsilicon-containing organic fluoropolymers contains a silicon-containingorganic fluoropolymer wherein the g is an integer of 2 or above:

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R² represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; and m represents 1, 2 or 3.15. A water-repellent glass member which comprises a glass substrateand, as formed on the glass surface, a layer of a silicon-containingorganic fluoropolymer represented by the general formula (Ix):

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R² represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; m represents 1, 2 or 3; andn_(x) represents an integer of 2 or above.
 16. A process for preparing awater-repellent glass member, which comprises coating the glass surfacewith a treating solution comprising a mixture of silicon-containingorganic fluoropolymers represented by the general formula (Ia) andhaving a number average molecular weight of from 5×10² to 1×10⁵, whereing is 0 or an integer of 1 or above and the mean value of the g isgreater than 1 in said mixture provided said mixture ofsilicon-containing organic fluoropolymers contains a silicon-containingorganic fluoropolymer wherein the g is an integer of 2 or above:

wherein Rf represents perfluoroalkyl; Z represents fluoro ortrifluoromethyl; a, b, c, d and e each independently represent 0 or aninteger of 1 or above, provided that a+b+c+d+e is not less than 1 andthe order of the repeating units parenthesized by subscripts a, b, c, dand e occurring in the formula is not limited to that shown; Yrepresents hydrogen or alkyl containing 1 to 4 carbon atoms; Xrepresents hydrogen, bromo or iodo; R¹ represents hydroxy or ahydrolyzable substituent group; R2 represents hydrogen or a monovalenthydrocarbon group; 1 represents 0, 1 or 2; and m represents 1, 2 or 3.